JP5853124B2 - Conductive shaft, conductive roll for OA equipment using the same, and method for producing conductive shaft - Google Patents

Description

  The present invention relates to a conductive shaft made of fiber reinforced resin (FRP), a conductive roll for OA equipment using the same, and a method for producing the conductive shaft.

  For conductive rolls (charging rolls, developing rolls, etc.) for OA (Office Automation) equipment such as electrophotographic copying machines, printers, facsimiles, etc., usually a shaft made of metal such as iron (shaft) ) Is used. Further, the shaft body is usually subjected to a plating treatment for preventing corrosion. The reason why the shaft made of metal is used for the conductive roll as described above is that high-precision workability and conductivity associated with the charging mechanism are required.

  However, the plating applied to the shaft is likely to be peeled off due to rubbing between shaft bodies during transportation or rubbing with abrasive powder, and as a result, there is a concern that the shaft may be corroded.

  In addition, the weight of the shaft is required to be easily transported, and further, the shaft is required to be non-magnetic so as not to adversely affect the aircraft instrument during air transportation. Furthermore, there is an environmental demand for reducing the amount of environmentally hazardous substances contained in the plating as much as possible.

  From the above, in recent years, a conductive roll using a resin shaft as a shaft instead of a metal shaft has been proposed (see Patent Document 1). That is, since it is made of resin, it does not contain heavy metals, does not rust, and is lightweight, so it is possible to solve the above-mentioned problem of the metal shaft.

JP 2003-195601 A

  However, the resin shaft has problems in terms of strength and rigidity, and has a low electrical conductivity and a large electrical loss compared to a metallic shaft, so that it cannot withstand practical use as a shaft body of a conductive roll. There's a problem. In addition, when imparting conductivity to a resin shaft, usually, a method of increasing the conductivity by adding a conductive filler such as carbon black to the resin composition that is the material is used. If the amount of addition is increased, the viscosity of the resin composition increases, which makes it difficult to mold. In particular, in the case of producing by injection molding as in the shaft disclosed in Patent Document 1, when a large amount of carbon black is added, the viscosity of the resin composition extremely increases so that injection molding becomes difficult. It is difficult to develop conductivity by addition. In addition, carbon black is inexpensive among conductive fillers, so it has a high cost merit. However, compared with other conductive fillers, the particles are smaller and have a larger surface area. There is also a problem that sex is difficult to express.

  Therefore, the present inventors examined a shaft made of fiber reinforced resin (FRP) using only conductive carbon fiber (CF) as a reinforcing material. However, carbon fiber (CF) is very expensive, and therefore has a problem of greatly affecting the unit price of products.

  The present invention has been made in view of such circumstances, and is a light-weight, high-strength, excellent-conductive, and inexpensive, a conductive shaft, a conductive roll for OA equipment using the same, and a conductive property. The purpose is to provide a manufacturing method for the shaft.

In order to achieve the above object, the present invention is a fiber-reinforced resin shaft in which a continuous glass fiber bundle is embedded in parallel to the longitudinal direction of the shaft, and the matrix resin is composed mainly of the following (A): And a resin composition containing the following components (B) to (D), wherein the component (B) is particulate and is distributed along the continuous glass fibers constituting the continuous glass fiber bundle. A shaft is a first gist, and a conductive roll for office automation equipment having the conductive shaft as a shaft is a second gist.
(A) Thermosetting resin.
(B) Carbon black.
(C) A dispersant having a basic functional group.
(D) Curing agent for component (A).

Moreover, this invention is a manufacturing method of the said electroconductive shaft, Comprising: The resin composition which contains the following (A) as a main component in the state which bundled the continuous glass fiber, and contained the following (B)-(D) component Is drawn into a tank containing the glass fiber, impregnated with continuous glass fiber in a resin composition, and then drawn into a mold and thermally cured, and the resulting long fiber reinforced resin molded product is cut into a predetermined length. A method for producing a conductive shaft is a third aspect.
(A) Thermosetting resin.
(B) Carbon black.
(C) A dispersant having a basic functional group.
(D) Curing agent for component (A).

  That is, the present inventors have intensively studied to solve the above problems. In the course of the research, the present inventors made a continuous fiber bundle made of glass fiber (GF) having a higher cost merit than carbon fiber (CF) as the reinforcing material made of a shaft made of fiber reinforced resin. It was considered that a continuous glass fiber bundle was embedded in parallel to the longitudinal direction of the shaft, and that the matrix resin contained carbon black in order to impart conductivity. However, when carbon black is used, it is necessary to solve the problems relating to formability and conductivity imparting as described above. Therefore, the present inventors have further researched, and the matrix resin composition is composed of a thermosetting resin (A) as a main component and a dispersant having a basic functional group (C). The basic functional group of the dispersant (C) interacts with the acidic functional group of the carbon black (B), the dispersibility of the carbon black (B) is improved, and the carbon black (B) is interposed between the continuous glass fiber bundles. I found out that it was going in and arranged. As a result, the carbon black (B) is distributed along the continuous glass fibers constituting the continuous glass fiber bundle in the form of particles, and an electric pass route can be created without increasing the viscosity of the composition with a small amount of carbon black. As a result, it was found that a conductive shaft capable of achieving the intended purpose was obtained, and the present invention was achieved.

In addition, it is difficult to make an electric path route with a small amount of carbon black as described above by conventional injection molding. Therefore, in a state where the continuous glass fiber is bundled, it is drawn into the tank containing the matrix resin composition, impregnated with the continuous glass fiber into the resin composition, and then drawn into a mold and thermally cured, and the length obtained thereby. Applying a special manufacturing method such as cutting a fiber-reinforced resin molded product of a length to a predetermined length, the above problem is solved, and a special conductive shaft as described above can be manufactured well. The inventors have determined that they can do this.

  As described above, the conductive shaft of the present invention is a fiber-reinforced resin shaft in which a continuous glass fiber bundle is embedded in parallel to the longitudinal direction of the shaft, and the matrix resin is a thermosetting resin (A). Is a resin composition containing carbon black (B), a specific dispersant (C), and a curing agent (D), and the carbon black (B) is a particulate and continuous glass fiber bundle. It is distributed along the continuous glass fiber which comprises. Therefore, it is possible to provide a conductive shaft that is lightweight, high in strength, excellent in conductivity, and inexpensive. Moreover, the conductive roll for OA equipment using the said conductive shaft used the said conductive shaft like the weight reduction etc. while exhibiting the outstanding roll performance similarly to what used the conventional metal shaft. The effect by this can be obtained.

Further, in a state where the continuous glass fibers are bundled, they are drawn into a tank containing the resin composition, impregnated with the continuous glass fibers into the resin composition, and then drawn into a mold and thermally cured, and the long length obtained thereby. By using a special manufacturing method such as cutting the fiber reinforced resin molded product into a predetermined length, an electric path route can be formed with a small amount of carbon black, and the conductive shaft of the present invention can be manufactured satisfactorily.

It is the schematic diagram which showed the cross-sectional state of the electroconductive shaft of this invention. It is the schematic diagram which showed the cross-sectional state of the shaft for a comparison.

  Next, embodiments of the present invention will be described in detail.

  As described above, the conductive shaft of the present invention is a fiber-reinforced resin shaft in which a continuous glass fiber bundle is embedded in parallel to the longitudinal direction of the shaft, and the matrix resin is a thermosetting resin ( A) comprising a resin composition comprising as a main component carbon black (B), a specific dispersant (C) and a curing agent (D), wherein the carbon black (B) is in the form of particles and continuous glass fibers It is distributed along the continuous glass fibers constituting the bundle. Here, the “main component” of the resin composition has a great influence on the properties of the entire composition, and means 50% by weight or more of the total in the present invention. In addition, “the carbon black (B) is distributed along the continuous glass fibers that are in the form of particles and constitute a continuous glass fiber bundle.” Along with this, an electric path route is formed by carbon black, which means that the conductivity of the shaft is secured. This is schematically shown in FIG. In the figure, 1 is a shaft, 2 is a glass fiber bundle, 2a is a glass fiber constituting it, 3 is carbon black, and 4 is a matrix resin. The distribution state of the carbon black can be confirmed by observing the cross section of the conductive shaft with an electron microscope. Usually, the mixing ratio of the carbon black in the resin composition that is the material of the matrix resin is described later. If the electric resistance value of the conductive shaft shows a low value as described later, the carbon black can be regarded as being in the distribution state as described above. FIG. 2 is a diagram for comparison, and shows how carbon black is aggregated without being in the distribution state as described above.

  In the conductive shaft of the present invention, the glass fiber needs to be a continuous fiber from the viewpoint of strength and rigidity as described above, and is bundled as described above. In addition, the glass fiber content rate (Vf value) in the electroconductive shaft of this invention calculated | required by the following formulas (1) becomes like this. Preferably it is 40 to 70%, More preferably, it is 55 to 65%. That is, if the Vf value is too small, there is a risk that the product will have severe molding shrinkage and there will be no surface smoothness. Conversely, if the Vf value is too large, the amount of resin will decrease and the conductivity may not be ensured. Because.

  In the conductive shaft of the present invention, examples of the thermosetting resin (A) constituting the resin composition that is the material of the matrix resin include unsaturated polyester resins, vinyl ester resins, epoxy resins, and phenol resins. It is done. These may be used alone or in combination of two or more. Of these, unsaturated polyester resins are preferred from the viewpoint of adhesion to glass fibers.

  As the curing agent (D) of the thermosetting resin (A), for example, unsaturated polyester resin and vinyl ester resin include methyl ethyl ketone peroxide, acetylacetone peroxide, benzoyl peroxide, tertiary butyl peroxide-2- Organic peroxides such as ethyl hexanoate, benzoyl peroxide, tertiary butyl perbenzoate and dicumyl peroxide are used. Epoxy resins include bisphenol A, tetrabromobisphenol A, bisphenol S, bisphenol F, bis ( 4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) ethane, 1,3,3-trimethyl-1-m-hydroxyphenylindan-5-ol, 1,3,3-trimethyl-1-m-hydroxy Enylindane-7-ol, 1,3,3-trimethyl-1-p-hydroxyphenylindan-6-ol, resorcin, hydroquinone, catechol, nadic acid, maleic acid, phthalic acid, methyl-tetrahydrophthalic acid, methyl nadic acid, etc. Polycarboxylic acids and their anhydrides, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenyl ether, phenylenediamine, diaminodicyclohexylmethane, xylylenediamine, toluenediamine, diaminodicyclocyclohexane, dichloro-diaminodiphenylmethane (including isomers), ethylenediamine Polyamine compounds such as hexamethylenediamine, dicyandiamide, tetramethylguanidine, active hydrogen-containing compounds capable of reacting with epoxy groups, etc. The Nord resin, hexamethylene tetramine, melamine and methylol urea, or the like is used. These may be used alone or in combination of two or more. The ratio of the curing agent (D) in the resin composition is preferably in the range of 0.5 to 15 parts by weight, more preferably 100 parts by weight with respect to 100 parts by weight of the thermosetting resin (A), more preferably. Is in the range of 1 to 10 parts by weight.

The carbon black (B) used together with the thermosetting resin (A) has an average particle diameter (primary particle diameter) of preferably 18 to 122 nm, more preferably 27 to 43 nm, from the viewpoint of wettability of the resin. Is used. Further, the carbon black (B), from the viewpoint of electrical conductivity (electrical path route formation), the DBP oil absorption is preferably 42~495m ² / g, more preferably those 160~360m ² / g used . The DBP oil absorption is defined in JIS K 6217, and specific examples of the carbon black include acetylene black and ketjen black. These may be used alone or in combination of two or more. Among these, acetylene black is preferable from the viewpoints of the wettability of the resin and the conductivity (formation of electric path route).

  The proportion of carbon black (B) in the resin composition is preferably in the range of 5 to 15 parts by weight with respect to 100 parts by weight of the thermosetting resin (A). That is, if the amount of the carbon black (B) is too small, sufficient conductivity cannot be obtained. Conversely, if the amount of the carbon black (B) is too large, the viscosity of the resin composition increases. This is because the resin composition is not completely impregnated in the fiber bundle, and the moldability is deteriorated and the conductivity is adversely affected.

  As the specific dispersant (C) used together with the thermosetting resin (A) and carbon black (B), a dispersant having a basic functional group is used. Here, the “dispersant” in the present invention means that the dispersibility in the thermosetting resin (A) is improved by adsorbing to the surface of the carbon black (B), and the carbon black (B) is regenerated over time. What suppresses aggregation is used. Examples of the basic functional group in the dispersant include an amino group and an amine group because they easily act on the carbon black (B).

  In addition, it is preferable that the dispersant (C) further has a structure having an affinity for the thermosetting resin (A) from the viewpoint of further improving the dispersion stability of the carbon black (B). The “structure having affinity with the thermosetting resin (A)” differs depending on the type of the thermosetting resin (A). For example, as the thermosetting resin (A), an unsaturated polyester resin is used. When the vinyl ester resin is used, as the dispersing agent (C), polymeric polymer components such as boric acid ester, alkylammonium salt of polycarboxylic acid, unsaturated polycarboxylic acid polymer, unsaturated fatty acid polyamine amide and acidic ester Use what has. When an epoxy resin and a phenol resin are used as the thermosetting resin (A), the dispersant (C) is an alkyl ammonium salt of a polycarboxylic acid, an unsaturated polycarboxylic acid polymer, an unsaturated fatty acid polyamine amide, and an acid. Those having a polymer component such as an ester are used.

  In addition, even if the dispersant (C) does not have a structure having an affinity for the thermosetting resin (A), it has a structure having an affinity for the thermosetting resin (A). By using a dispersant (a dispersant not corresponding to (C)) in combination with the dispersant (C), the same effect (the dispersion stability effect of the carbon black (B)) can be obtained. In addition, when using this dispersing agent, it is preferable that the ratio is the range of 1.45-3.78 weight part with respect to 100 weight part of thermosetting resins (A).

  And as for the said dispersing agent (C), BYK-9076 (alkyl ammonium salt) by a BYK company, SOLPERSE5000 (a copper phthalocyanine sulfonic acid ammonium salt) by Nippon Lubrizol, etc. are mention | raise | lifted by the commercial item, for example.

  Moreover, as for the dispersing agent which has a structure with affinity with a thermosetting resin (A), but does not have a basic functional group, SOLSPERSE88000 by Nippon Lubrizol is mentioned as a commercial item.

  The proportion of the dispersant (C) in the resin composition is preferably in the range of 5 to 15 parts by weight with respect to 100 parts by weight of the thermosetting resin (A) when used alone. In addition, when used in combination with a dispersant having a structure having an affinity for the thermosetting resin (A) but not having a basic functional group, the proportion of the dispersant (C) is 100 wt% of the thermosetting resin (A). The amount is preferably 1.45 to 3.78 parts by weight with respect to parts. That is, if the amount of the dispersing agent (C) is too small, the viscosity of the resin composition becomes high and sufficient dispersion stability of the carbon black (B) cannot be obtained, and desired conductivity cannot be expressed. On the contrary, if the amount of the dispersant (C) is too large, there will be an excess dispersant that does not act on the carbon black (B), and the spacing between the particulate carbon blacks distributed along the fiber bundle This is because the spread is too large and the desired conductivity cannot be expressed.

  Note that the resin composition includes a curing (crosslinking) accelerator, a curing (crosslinking) accelerator auxiliary, an auxiliary agent, a plasticizer, an anti-aging agent, an anti-shrinkage agent, an ozone deterioration preventing agent, and an antifoam as necessary. Agents, sag-preventing agents, organic solvents, inorganic fillers (talc, mica, calcium carbonate, kaolin, wollastonite, milled fiber) and the like may be added as appropriate.

  Next, the conductive shaft of the present invention is manufactured as follows, for example.

That is, a resin composition containing a thermosetting resin (A) as a main component and a curing agent (D), carbon black (B), and a specific dispersant (C) in a state where continuous glass fibers are bundled. Is drawn into a tank containing the glass fiber, impregnated with continuous glass fiber in a resin composition, and then drawn into a mold and thermally cured, and the resulting long fiber reinforced resin molded product is cut into a predetermined length. . Also, after impregnating the continuous glass fiber into the resin composition, when pulling it into the mold, a nonwoven fabric (polyester, glass, and aramid types are available as materials) to suppress exposure to the fiber surface. May be set. By such a special manufacturing method, an electric path route can be formed with a small amount of carbon black, and the target conductive shaft of the present invention can be manufactured satisfactorily.

  In particular, it is preferable to knead the resin composition used for the impregnation treatment with three rolls because the aggregation of carbon black is further eliminated and the conductivity of the resulting conductive shaft can be further increased. The kneading treatment is performed before the curing agent is added, and the kneading is performed again after the curing agent is added. At this time, kneading may be performed by hand stirring, feathering, or the like because the curing agent may be mixed in the resin composition. Any of agitation and kneading by rolls may be used. Among these, feather stirring is simple and preferable.

  Moreover, it is preferable to make the viscosity of the resin composition used for the impregnation treatment in the range of 0.5 to 60 Pa · s because the special production method can be performed satisfactorily. In addition, the said viscosity is measured before adding a hardening | curing agent, and is a value measured by temperature: room temperature (28 to 35 degreeC) using the B-type viscosity meter based on JISK7117. .

  The resin composition subjected to the impregnation treatment is thermally cured in a mold at 100 to 160 ° C. by heat treatment for about 1 to 15 minutes.

  The long fiber-reinforced resin molded product obtained by thermosetting in the mold is cut into a predetermined length by a cutting machine or the like, and becomes a target conductive shaft.

  The series of manufacturing methods can be performed using a general pultrusion machine.

  Moreover, it is preferable to appropriately form a conductive coating layer made of metal plating, metal powder, or graphite on the surface of the shaft. That is, when the conductive coating layer is formed as described above, the possibility that continuous glass fibers are exposed on the surface of the shaft is eliminated, the conductivity of the shaft surface is easily developed, and the bending rigidity of the shaft is improved. Because it will be. Further, by supplementing the conductivity of the shaft with the conductive coating layer, the amount of carbon black in the resin composition used for the impregnation treatment of the continuous glass fiber at the time of producing the shaft can be further suppressed. As a result, the increase in viscosity of the resin composition can be suppressed and the shaft can be more easily formed by pultrusion, so that the productivity of the shaft can be further improved. The conductive coating layer may be formed only on the outer peripheral surface (side surface) of the shaft, but it is preferable that the conductive coating layer be formed on the end surface of the shaft, that is, the cut surface of the shaft. That is, when the conductive coating layer is also formed on the surface of the end portion of the shaft as described above, the conductivity between the end portion of the shaft and the outer peripheral surface is favorably expressed. By the way, the shaft surface includes both the shaft outer peripheral surface and the shaft end surface.

  When the conductive coating layer is formed by metal plating, for example, it can be formed by applying electrolytic plating or electroless plating such as zinc-nickel plating or nickel plating to the shaft surface according to a conventional method. When the conductive coating layer is formed of metal powder or graphite, for example, a coating liquid in which metal powder or graphite powder made of SUS, aluminum or the like is dispersed in an organic solvent is applied to the shaft surface and dried. By doing so, the conductive coating layer can be applied. The conductive coating layer may be formed as described above with a coating liquid in which the metal powder and the graphite powder are mixed and dispersed. In addition, from the viewpoint of increasing the coating film strength, the coating liquid may appropriately contain a resin binder such as urethane, epoxy, acrylic, and polyester. However, in terms of conductivity, such a resin binder may be added. It is preferable not to contain it. Further, the surface of the shaft before coating may be roughened by etching in advance to improve the fixing property of the conductive coating layer. The etching process is performed by a chemical process such as an alkaline solution or a hydrofluoric acid solution, or a physical process such as wet blasting.

The conductive shaft of the present invention obtained as described above sufficiently exhibits its function as a shaft body of a conductive roll for OA equipment when its electrical resistance value is less than 1 × 10 ⁶ Ω. Is preferable.

  And the conductive roll for OA equipment which uses the conductive shaft of this invention as a shaft body originates in the performance of the shaft body, and has an excellent function as a conductive roll for OA equipment (especially a charging roll and a developing roll). It can be demonstrated.

  The conductive shaft of the present invention exhibits excellent performance as a shaft body for rolls for OA equipment such as a toner supply roll, a paper feed roll, a transfer roll, and a cleaning roll in addition to a charging roll and a developing roll. Can do. In addition, the conductive shaft of the present invention can be used as a shaft body for industrial rolls such as dustproof rolls and engraving rolls, and also as structural members for various products.

  Next, examples will be described together with comparative examples. However, the present invention is not limited to these examples as long as the gist thereof is not exceeded.

  First, prior to the examples and comparative examples, the following materials were prepared.

[Thermosetting resin (A1)]
Unsaturated polyester resin (Iupica 3140, manufactured by Nippon Iupika)

[Carbon black (B1)]
Denka Black (average particle size 35 nm, DBP oil absorption 160 ml / 100 g), manufactured by Denka

[Carbon black (B2)]
Seast TA (average particle size 122 nm, DBP oil absorption 42 ml / 100 g), manufactured by Tokai Carbon Co., Ltd.

[Dispersant (C1)]
Alkyl ammonium salt (BYK-9076, manufactured by BYK)

[Dispersant (C2)]
Copper phthalocyanine sulfonate ammonium salt (SOLSPERSE 5000, manufactured by Nippon Lubrizol)

[Dispersant (C3)]
SOLPERSE 88000, manufactured by Nihon Lubrizol

[Dispersant (C4) (for comparative example)]
Copolymer having acid groups (BYK-W9010, manufactured by BYK)

[Dispersant (C5) (for comparative example)]
Spherical block copolymer (DISPERBYK-2155, manufactured by BYK)

[Curing agent (D1)]
Parroyl TCP, NOF Corporation

[Examples 1-9, Comparative Examples 1-3]
The thermosetting resin and the dispersant were blended, and after stirring the wings, carbon black was added and kneaded with a three roll. Then, the hardening | curing agent was added and feather stirring was performed and the resin composition was prepared. The mixing ratio of the above components and the three-roll gap during the kneading were as shown in Tables 1 and 2 below.

Subsequently, in a state where the continuous glass fibers are bundled, the continuous glass fibers are drawn into the tank containing the resin composition prepared above, impregnated with the continuous glass fibers into the resin composition, and then drawn into a mold to be thermally cured. The long fiber reinforced resin molded product was cut to produce a shaft having a diameter of 6 mm and a length of 300 mm. In addition, the shaft was produced so that the glass fiber content (Vf value) of the shaft calculated | required by the following formulas (1) may become as shown in Table 1 and Table 2 of a postscript.

  With respect to the shafts of Examples and Comparative Examples thus obtained, each characteristic was measured and evaluated according to the following criteria. The results are shown in Tables 1 and 2 below.

(Viscosity measurement)
The viscosity (viscosity before adding the curing agent) of the resin composition after kneading with the three rolls was measured under the following conditions.
・ Device: manufactured by TOKI SANGYO, VISCOMETER TVB-10 (TVR) ・ Rotor type: H7
・ Rotation speed: 60rpm
・ Measurement environment: Room temperature (28 ℃ ~ 35 ℃)

(Electric resistance measurement)
The electrical resistance value varies depending on the shape (cross-sectional area and length) to be evaluated. Therefore, the shape of the shaft was unified to a diameter of 6 mm and a length of 300 mm, and the electric resistance value was measured using a tester (MODEL 3021, manufactured by HIoki Corporation). The measurement was performed by applying a measuring needle to the end section of the shaft having the above shape. And when the electrical resistance value was less than 1 × 10 ³ Ω, the case where it was 1 × 10 ³ Ω or more and less than 1 × 10 ⁶ Ω was evaluated as ○, and 1 × 10 ⁶ Ω or more was evaluated as ×. .

  From the above results, it can be seen that the shafts of Examples 1 to 9 have lower electrical resistance values and superior conductivity than the shafts of the comparative examples. In addition, in the comparative example, when the blending amount of carbon black was further increased, a rapid increase in viscosity of the resin composition (60 Pa · s or more) was observed, and the shaft was applied by applying the molding methods of the examples and comparative examples. Could not be manufactured.

[Example 10]
A conductive coating layer was formed on the entire surface of the shaft produced in the same manner as in Example 1 by the following coating treatment 1.
[Coating treatment 1]
First, the shaft was etched for 10 minutes at a temperature of 40 ° C. using a 200 g / L NaOH aqueous solution. Next, the shaft was immersed in a Pd catalyst imparting agent (OPC-50 inducer, Okuno Pharmaceutical Co., Ltd.) at 40 ° C. for 5 minutes to impart a Pd catalyst to the surface. Subsequently, the shaft was immersed in an activator (OPC-150 crystal, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25 ° C. for 5 minutes to metallize Pd ions (activation treatment). Thus, after pre-plating the entire surface of the shaft, the shaft was immersed in an electroless nickel plating solution (TMP Chemical Nickel HRT, manufactured by Okuno Pharmaceutical Co., Ltd.) for 10 minutes at 40 ° C. A 5 μm electroless nickel plating layer (conductive coating layer) was formed.

[Example 11]
A conductive coating layer was formed on the entire surface of the shaft produced in the same manner as in Example 4 by the coating treatment 1 described above.

[Example 12]
A conductive coating layer was formed on the entire surface of the shaft produced in the same manner as in Example 6 by the coating treatment 1 described above.

[Example 13]
A conductive coating layer was formed on the entire surface of the shaft produced in the same manner as in Example 6 by the following coating treatment 2.
[Coating process 2]
Spray the entire surface of the shaft with a spray agent (graphite spray, manufactured by Fine Chemical Japan Co., Ltd.) in which graphite powder is dispersed in an organic solvent such as isopropanol, dimethyl ether, etc., dry at room temperature for about 1 hour, and then dry at 60 ° C. To form a conductive coating layer.

[Example 14]
A conductive coating layer was formed on the entire surface of the shaft produced in the same manner as in Example 6 by the following coating treatment 3.
[Coating 3]
Spray the whole surface of the shaft with a spray agent (stainless steel spray, manufactured by Fine Chemical Japan Co., Ltd.) in which SUS powder is dispersed in an organic solvent such as toluene or dimethyl ether, and dry at room temperature for about 1 hour. To form a conductive coating layer.

[Example 15]
A conductive coating layer was formed on the entire surface of the shaft produced in the same manner as in Example 6 by the following coating treatment 4.
[Coating treatment 4]
A spray agent (fine heat reflector, manufactured by Fine Chemical Japan Co., Ltd.) in which aluminum powder is dispersed in an organic solvent such as toluene or dimethyl ether is sprayed on the entire surface of the shaft, dried at room temperature for about 1 hour, and then further heated to 60 ° C. And dried to form a conductive coating layer.

[Example 16]
A conductive coating layer was formed on the entire surface of the shaft produced in the same manner as in Example 6 by the following coating treatment 5.
[Coating treatment 5]
A spray agent (non-seeds, manufactured by Fine Chemical Japan Co., Ltd.) in which graphite powder and aluminum powder are mixed and dispersed in an organic solvent such as butane and propanol is sprayed on the entire surface of the shaft. It was dried at 0 ° C. to form a conductive coating layer.

  From the above results, it can be seen that the shafts of Examples 10 to 16 have lower electrical resistance values and are more excellent in conductivity than the shafts of Examples 1 to 9.

On the other hand, when the flexural modulus of the shaft was measured according to the following criteria, the flexural modulus of Example 10 was 43 GPa while the flexural modulus of Example 10 was 46 GPa. The flexural modulus of Example 12 was 43 GPa, whereas the flexural modulus of Example 11 was 46 GPa. Furthermore, the flexural modulus of Example 6 was 52 GPa, whereas the flexural modulus of Example 12 was 56 GPa. Thus, the improvement effect of the bending elastic modulus was recognized by formation of the conductive coating layer.
(Flexural modulus)
A shaft sample with a diameter of 6 mm and a length of 125 mm is standardized in accordance with JIS K7017 at a temperature of 25 ° C, and the shaft is subjected to a three-point bending test (indenter radius: 5 mm, support base radius: 2 mm, distance between supporting points) : 100 mm, test speed: 50 mm / min), and the flexural modulus (GPa) was measured.

  In addition, in the said Example, although it showed about the specific form in this invention, the said Example is only a mere illustration and is not interpreted limitedly. Various modifications apparent to those skilled in the art are contemplated to be within the scope of this invention.

  The conductive shaft of the present invention is lightweight, high in strength, excellent in conductivity, and inexpensive. Therefore, it is preferably used as a shaft body of a conductive roll for OA equipment, but in addition, a shaft body of a roll for OA equipment that does not require conductivity, a shaft body of an industrial roll such as a dustproof roll, an engraving roll, It can also be used as a structural member for various products.

1 Shaft 2 Glass fiber bundle 2a Glass fiber 3 Carbon black 4 Matrix resin

Claims (15)

A fiber reinforced resin shaft in which a continuous glass fiber bundle is embedded in parallel to the longitudinal direction of the shaft, and the matrix resin contains the following (A) as a main component and the following (B) to (D) components: A conductive shaft comprising the resin composition contained therein, wherein the component (B) is particulate and distributed along continuous glass fibers constituting a continuous glass fiber bundle.
(A) Thermosetting resin.
(B) Carbon black.
(C) A dispersant having a basic functional group.
(D) Curing agent for component (A).   The conductive shaft according to claim 1, wherein the dispersant (C) further has a structure having an affinity with the thermosetting resin (A).   The conductive shaft according to claim 1 or 2, wherein the thermosetting resin (A) is at least one selected from the group consisting of an unsaturated polyester resin, a vinyl ester resin, an epoxy resin, and a phenol resin.   The ratio of carbon black (B) in the said resin composition is the range of 5-15 weight part with respect to 100 weight part of thermosetting resins (A), The electroconductivity as described in any one of Claims 1-3. shaft.   The ratio of the dispersing agent (C) in the said resin composition is the range of 5-15 weight part with respect to 100 weight part of thermosetting resins (A), The electroconductivity as described in any one of Claims 1-4. shaft.   The conductive composition according to any one of claims 1 to 5, wherein the resin composition further contains a dispersant having a structure having an affinity for the thermosetting resin (A) but not having a basic functional group. Sex shaft.   The resin composition further includes a dispersant having a structure having an affinity for the thermosetting resin (A) but not having a basic functional group, and the dispersant (C) in the resin composition. 5. The conductive shaft according to claim 1, wherein the ratio is in the range of 1.45 to 3.78 parts by weight with respect to 100 parts by weight of the thermosetting resin (A).   The conductive shaft according to any one of claims 1 to 7, wherein a conductive coating layer made of metal plating, metal powder, or graphite is further formed on the surface of the conductive shaft. The conductive shaft according to any one of claims 1 to 8, which has an electric resistance value of less than 1 x 10 ⁶ Ω.   The electroconductive shaft as described in any one of Claims 1-9 which is a shaft body of the electroconductive roll for OA equipment.   The electroconductive roll for OA equipment which uses the electroconductive shaft of Claim 10 as a shaft body.   The electroconductive roll for OA equipment of Claim 11 used for a charging roll or a developing roll. It is a manufacturing method of the electroconductive shaft as described in any one of Claims 1-10, Comprising: In the state which bundled continuous glass fiber, following (A) is a main component and following (B)-(D) component Is drawn into a tank containing a resin composition containing the resin composition, impregnated with continuous glass fiber into the resin composition, and then drawn into a mold and thermally cured, and a long fiber-reinforced resin molded product obtained thereby is predetermined. A method for producing a conductive shaft, characterized by being cut into lengths.
(A) Thermosetting resin.
(B) Carbon black.
(C) A dispersant having a basic functional group.
(D) Curing agent for component (A).   The method for producing a conductive shaft according to claim 13, wherein the resin composition used in the impregnation treatment is kneaded with a three-roll.   The method for producing a conductive shaft according to claim 13 or 14, wherein the resin composition used for the impregnation treatment has a viscosity in the range of 0.5 to 60 Pa · s.

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